PyCon is definitely an experience worth having if you are a Python programmer. There are so many interesting talks that you'll find yourself having to decide what is most important to you. Most (all?) of the talks have the audio recorded and posted on the PyCon website. So you probably won't miss anything. This is the second year that I have attended and I intend on returning for as long as they have it.
The Python community is very open and welcoming. This is one of its greatest assets. The Python celebrities and book authors are walking around in the crowd and are friendly and helpful. I remember attending Java conferences where certain people felt that they were some sort of royalty and that all the attendees where just commoners. This is the exact opposite of the PyCon vibe.
I met a lot of interesting people. Since I am terrible at keeping track of names and email addresses I having a hard time getting back to everyone. If we talked at PyCon feel free to email me to say hi.